CN104393259A - Preparation method of porous carbon ball-supported MxOy nanoparticle composite material - Google Patents
Preparation method of porous carbon ball-supported MxOy nanoparticle composite material Download PDFInfo
- Publication number
- CN104393259A CN104393259A CN201410535742.4A CN201410535742A CN104393259A CN 104393259 A CN104393259 A CN 104393259A CN 201410535742 A CN201410535742 A CN 201410535742A CN 104393259 A CN104393259 A CN 104393259A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon ball
- mxoy
- preparation
- nano composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a porous carbon ball-supported MxOy nanoparticle composite material. The preparation method comprises the following steps of weighing porous carbon balls, adding the porous carbon balls into a solvent, carrying out ultrasonic dispersion, carrying out heating for a reaction, adding a proper amount of acetylacetone salt into the reaction product at a required temperature, carrying out a high-temperature backflow reaction process, then carrying out centrifugation and washing, and collecting the product which is the porous carbon ball-supported MxOy nanoparticle composite material, wherein M represents Mn, Fe or Co. The preparation method has simple processes and general preparation conditions. The porous carbon ball-supported MxOy nanoparticle composite material has stable product morphology and high purity and can be treated conveniently and simply. The preparation method is suitable for middle-scale industrial production.
Description
Technical field
The invention belongs to field of material technology, particularly relate to a kind of preparation method of porous carbon ball load MxOy (M=Mn, Fe, Co) nano composition.
Background technology
Lithium ion battery is as an effective sustainable stored energy system, there is the advantages such as volume is little, quality is light, capacitance is large, voltage is high, safe, pollution-free, become the current internationally recognized desirable chemical energy, be widely used in the electronic products such as mobile phone, notebook computer, electric tool and mobile communications tool, be expected to future realize large-scale application in fields such as electric automobile, space flight and aviation, military mobile communication facility and equipment.Wherein, the oxide of manganese, iron, cobalt is (as Mn
3o
4, Fe
3o
4, CoO) as lithium ion battery negative material, there is high theoretical specific capacity, and rich reserves, environmentally safe, but because nano particle is easily reunited, cause in the discharge and recharge journey of battery, capacity sharply declines, and cycle performance is unstable, thus limit to its further development and application.
Namely the present invention is starting point from overcoming this quagmire, the hole wall of porous carbon ball is utilized to provide carrier for oxide nano-particles, metal oxide nanoparticles is carried on porous carbon ball, not only can overcome the reunion between metal oxide nanoparticles, the frame structure of porous carbon ball also can be utilized to provide the structural stability of composite material, utilize advantage common between them, greatly widen the range of application of metal oxide nanoparticles and porous carbon ball, in chemical power source, catalyst and pharmaceutical carrier and gas sensor etc., there is important using value.So explore the control synthetic method of simple, the effective metal oxide-loaded nano particle composite material of porous carbon ball, the investigation and application for this type of composite material has important theory and realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of porous carbon ball load MxOy (M=Mn, Fe, Co) preparation method of nano composition, technique is simple, prepared composite material effectively can suppress reunion and the volumetric expansion of oxide nano-particles, the lithium ion battery negative material prepared thus has excellent electric conductivity, and corresponding lithium ion battery specific capacity is high, good cycle.。
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of porous carbon ball load MxOy (M=Mn, Fe, x is 3, y is 4; M=Co, x, y are 1) preparation method of nano composition, concrete steps are as follows:
Take porous carbon ball and join ultrasonic disperse in solvent, mechanical agitation after being heated to 200 ~ 320 DEG C, add acetylacetonate, high temperature reflux reaction 0.5h ~ 2h, after carrying out three washings, centrifugation repeatedly after end, desciccate obtains porous carbon ball load MxOy (M=Mn, Fe, Co) nano composition; Wherein: the concentration range of described porous carbon ball is 0.2 ~ 1.0 mg/mL.
In the present invention, the preparation method of described porous carbon ball, concrete steps are as follows:
(1) after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce inert gas;
(2) import in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work by controlling inert gas flow velocity by droplet, by the process of body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle of discharging from quartz ampoule with absolute ethyl alcohol, centrifugation, drying obtain porous carbon ball, wherein:
The concentration range of described sodium chloroacetate is 0.5 ~ 2 mol/L;
Described inert gas is argon gas or nitrogen;
Described gas flow rate range is 0.5 ~ 2.5 L/min.
In the present invention, described solvent is triethylene glycol or institute's TEG.
In the present invention, described acetylacetonate is manganese acetylacetonate (III), and molecular formula is MnC
15h
21o
6;
Or described acetylacetonate is ferric acetyl acetonade (III), molecular formula is FeC
15h
21o
6;
Or described acetylacetonate is acetylacetone cobalt (II), molecular formula is CoC
10h
14o
4.
In the present invention, described MxOy, as M=Mn, is Mn
3o
4;
As M=Fe, be Fe
3o
4;
As M=Co, be CoO.
In the present invention, described washing is by deionized water and absolute ethyl alcohol washed product successively.
Owing to adopting such scheme, the present invention has following beneficial effect:
1, present invention achieves and utilize common acetylacetonate and the porous carbon ball prepared by high-temperature spray pyrolysismethod to be the presoma of reaction, porous carbon ball load MxOy (M=Mn has been synthesized first by one-step method, Fe, Co) nano composition.
2, the particle size of method of the present invention to the oxide nano particles of load in product has very high control.
3, the present invention adopts high temperature reflux method, has very strong versatility.
4, the product that prepared by the present invention is loose structure, and load nano particle is uniformly dispersed and is nano-scale, as lithium ion battery negative material, has height ratio capacity and high service life cycle, has comparatively vast potential for future development and application space.
5, technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product process is convenient succinct, is suitable for medium-scale industrial production.
6, method of the present invention have mild condition, homogeneous heating, productive rate efficient, be easy to the features such as control.
Accompanying drawing explanation
Fig. 1 is the SEM photo of porous carbon ball in embodiment 1, and scale is 200nm;
Fig. 2 is the SEM photo of composite material in embodiment 1, and scale is 200nm;
Fig. 3 is the XRD collection of illustrative plates of composite material in embodiment 1;
Fig. 4 is the SEM photo of composite material in embodiment 2, and scale is 200nm;
Fig. 5 is the XRD collection of illustrative plates of composite material in embodiment 2;
Fig. 6 is the SEM photo of composite material in embodiment 3, and scale is 200nm;
Fig. 7 is the XRD collection of illustrative plates of composite material in embodiment 3.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further detailed explanation.
Embodiment 1
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, continues to pass into 1.0L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 600 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is porous carbon ball.
2) porous carbon ball load Mn
3o
4the synthesis of nano composition
The first step, take after 25mg porous carbon ball is scattered in the triethylene glycol of 50mL, proceed in the three-neck flask of 100mL, mechanical splash bar is also heated to 250 DEG C;
Second step, in above-mentioned three-neck flask, add the 0.3523g manganese acetylacetonate (III) of precise, terminate after back flow reaction 2h at 250 DEG C, solution is cooled to room temperature;
3rd step, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load Mn
3o
4nano composition.
Fig. 1 is the SEM photo of porous carbon ball in embodiment 1, and scale is 200nm, can be observed the spherical homogeneous of porous carbon ball from picture, and duct is abundant and capacity is large, and specific area is large; Fig. 2 is the SEM photo of composite material in embodiment 1, and scale is 200nm, and comparison diagram 1 can be observed loaded particle uniform load in carbon ball wall surface, and load capacity is more; Fig. 3 is the XRD collection of illustrative plates of composite material in embodiment 1, with compound Mn
3o
4standard card (JCPDS NO.18-0803) is consistent, and illustrates that in compound, load particle is Mn
3o
4nano particle.
Embodiment 2
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes 11.6g sodium chloroacetate dissolved in 100mL deionized water, adds in humidifier, produces droplet;
Second step, continues to pass into 1.0L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is porous carbon ball.
2) porous carbon ball load Fe
3o
4the synthesis of nano composition
The first step, take after 30mg porous carbon ball is scattered in the triethylene glycol of 50mL, proceed in the three-neck flask of 100mL, mechanical splash bar is also heated to 270 DEG C;
Second step, in above-mentioned three-neck flask, add the 0.1765g ferric acetyl acetonade (III) of precise, terminate after back flow reaction 1h at 270 DEG C, solution is cooled to room temperature;
3rd step, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load Fe
3o
4nano composition.
Fig. 4 is the SEM photo of composite material in embodiment 2, and scale is 200nm, and comparison diagram 2 can be observed, and load capacity decreases, but load still homogeneous dispersion; Fig. 5 is the XRD collection of illustrative plates of composite material in embodiment 2, with compound F 17-hydroxy-corticosterone e
3o
4standard card (JCPDS NO.65-3107) is consistent, and illustrates that in compound, load particle is Fe
3o
4particle.
Embodiment 3
1) high-temperature spray pyrolysismethod prepares porous carbon ball
The first step, takes after 25mg porous carbon ball is scattered in the triethylene glycol of 50mL, proceeds in the three-neck flask of 100mL, add in humidifier, produce droplet;
Second step, continues to pass into 1.5L/min argon gas in humidifier, is imported by droplet in the tube furnace quartz ampoule of 700 DEG C of work;
3rd step, utilizes absolute ethyl alcohol to collect the gas of discharging from quartz ampoule;
4th step, centrifugal product under 5000rpm collecting precipitation, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is porous carbon ball.
2) synthesis of porous carbon ball load C oO nano composition
The first step, measures the triethylene glycol of 50mL in the three-neck flask of 100mL, and mechanical splash bar is also heated to 250 DEG C;
Second step, in above-mentioned three-neck flask, add the 0.2572g acetylacetone cobalt (II) of precise, terminate after back flow reaction 1h at 250 DEG C, solution is cooled to room temperature;
3rd step, under the rotating speed of 8000rpm, centrifugal product, and by deionized water and absolute ethyl alcohol washed product successively, last 60 DEG C of desciccates, products therefrom is porous carbon ball load C oO nano composition.
Fig. 6 is the SEM photo of composite material in embodiment 3, and scale is 200nm, and load capacity is considerable and dispersed as can be seen from FIG.; Fig. 7 is the XRD collection of illustrative plates of composite material in embodiment 3, is consistent with Compound C oO standard card (JCPDS NO.48-1719), illustrates that in compound, load particle is CoO nano particle.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (6)
1. a preparation method for porous carbon ball load MxOy nano composition, is characterized in that M described in MxOy nano composition is any one in Mn, Fe or Co, when M is Mn, Fe, x is 3, y is 4, when M is Co, x, y are 1, and concrete steps are as follows:
Take porous carbon ball and join ultrasonic disperse in solvent, mechanical agitation after being heated to 200 ~ 320 DEG C, add acetylacetonate, high temperature reflux reaction 0.5h ~ 2h, after carrying out three washings, centrifugation repeatedly after terminating, desciccate obtains porous carbon ball load MxOy nano composition; Wherein: the concentration range of described porous carbon ball is 0.2 ~ 1.0 mg/mL.
2. the preparation method of a kind of porous carbon ball load MxOy nano composition according to claim 1, it is characterized in that the preparation method of described porous carbon ball, concrete steps are as follows:
(1) after deionized water dissolving sodium chloroacetate, add in humidifier, produce droplet by atomization, and introduce inert gas;
(2) import in the tube furnace quartz ampoule of 500 ~ 800 DEG C of work by controlling inert gas flow velocity by droplet, by the process of body of heater, droplet fast dewatering shrinks the porous carbon ball being converted into solid;
(3) collect the solid particle of discharging from quartz ampoule with absolute ethyl alcohol, centrifugation, drying obtain porous carbon ball, wherein:
The concentration of described sodium chloroacetate is 0.5 ~ 2 mol/L;
Described inert gas is argon gas or nitrogen;
Described gas flow rate is 0.5 ~ 2.5 L/min.
3. the preparation method of a kind of porous carbon ball load MxOy nano composition according to claim 1, is characterized in that: described solvent is triethylene glycol or TEG.
4. the preparation method of a kind of porous carbon ball load MxOy nano composition according to claim 1, is characterized in that:
Described acetylacetonate is manganese acetylacetonate (III), and molecular formula is MnC
15h
21o
6;
Or described acetylacetonate is ferric acetyl acetonade (III), molecular formula is FeC
15h
21o
6;
Or described acetylacetonate is acetylacetone cobalt (II), molecular formula is CoC
10h
14o
4.
5. the preparation method of a kind of porous carbon ball load MxOy nano composition according to claim 1, it is characterized in that: in described MxOy, as M=Mn, is Mn
3o
4; As M=Fe, be Fe
3o
4; As M=Co, be CoO.
6. the preparation method of a kind of porous carbon ball load MxOy nano composition according to claim 1, is characterized in that: described washing is by deionized water and absolute ethyl alcohol washed product successively.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410535742.4A CN104393259B (en) | 2014-10-13 | 2014-10-13 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410535742.4A CN104393259B (en) | 2014-10-13 | 2014-10-13 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104393259A true CN104393259A (en) | 2015-03-04 |
CN104393259B CN104393259B (en) | 2017-01-25 |
Family
ID=52611123
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410535742.4A Expired - Fee Related CN104393259B (en) | 2014-10-13 | 2014-10-13 | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104393259B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105842288A (en) * | 2016-03-22 | 2016-08-10 | 苏州捷德瑞精密机械有限公司 | Porous gas sensitive nanomaterial and preparation method thereof |
CN107093709A (en) * | 2017-03-31 | 2017-08-25 | 同济大学 | A kind of porous carbon ball loads the preparation method of sulfide composite |
CN109755503A (en) * | 2018-12-13 | 2019-05-14 | 温州大学 | The preparation method and its application in lithium-sulfur cell that manganese sub-group compound/carbon pipe carries sulphur composite material |
CN113193191A (en) * | 2021-04-25 | 2021-07-30 | 浙江理工大学 | Manganous-manganic oxide nanocrystalline @3D honeycomb-shaped hierarchical porous network framework carbon composite material and preparation and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1794372A (en) * | 2005-10-31 | 2006-06-28 | 中国科学院上海硅酸盐研究所 | Magnetic composite powder for ferroferric oxide nanometer crystal modified carbon nanometer pipe and its preparation method |
WO2009149540A1 (en) * | 2008-06-10 | 2009-12-17 | National Research Council Of Canada | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
-
2014
- 2014-10-13 CN CN201410535742.4A patent/CN104393259B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1794372A (en) * | 2005-10-31 | 2006-06-28 | 中国科学院上海硅酸盐研究所 | Magnetic composite powder for ferroferric oxide nanometer crystal modified carbon nanometer pipe and its preparation method |
WO2009149540A1 (en) * | 2008-06-10 | 2009-12-17 | National Research Council Of Canada | Controllable synthesis of porous carbon spheres, and electrochemical applications thereof |
CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
Non-Patent Citations (1)
Title |
---|
SHUANGLING JIN等: "Facile synthesis of hierarchically structured Fe3O4/carbon micro-flowers and their application to lithium-ion battery anodes", 《JOURNAL OF POWER SOURCES》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105842288A (en) * | 2016-03-22 | 2016-08-10 | 苏州捷德瑞精密机械有限公司 | Porous gas sensitive nanomaterial and preparation method thereof |
CN107093709A (en) * | 2017-03-31 | 2017-08-25 | 同济大学 | A kind of porous carbon ball loads the preparation method of sulfide composite |
CN107093709B (en) * | 2017-03-31 | 2020-06-26 | 同济大学 | Preparation method of porous carbon sphere loaded sulfide composite material |
CN109755503A (en) * | 2018-12-13 | 2019-05-14 | 温州大学 | The preparation method and its application in lithium-sulfur cell that manganese sub-group compound/carbon pipe carries sulphur composite material |
CN113193191A (en) * | 2021-04-25 | 2021-07-30 | 浙江理工大学 | Manganous-manganic oxide nanocrystalline @3D honeycomb-shaped hierarchical porous network framework carbon composite material and preparation and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104393259B (en) | 2017-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104009205B (en) | A kind of hollow graphite alkene ball and its production and use | |
CN106058215B (en) | Dodecahedron porous C o3The preparation method of ZnC/C composite materials and the application in lithium ion battery | |
CN104103812A (en) | Composite flexible electrode material as well as preparation method and application thereof | |
CN104393259A (en) | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material | |
CN105098160A (en) | Hollow porous graphene-doped carbon/silicon nanofiber lithium battery anode material and preparation method thereof | |
CN103268929A (en) | Carbon/copper/metal oxide composite porous material and preparation method and application thereof | |
CN107123810B (en) | A kind of preparation method and applications based on nickel phosphide skeleton structure composite material | |
CN103643262A (en) | Method for deep eutectic solvent electrodeposition of lead powder | |
CN103165876A (en) | A preparation method and applications of a lithium battery material with high rate performance | |
CN104134783A (en) | Nano-NiS/graphene composite anode material and preparation method thereof | |
CN105514370B (en) | A kind of nickelic ternary material in-stiu coating method | |
CN104934236A (en) | Method of preparing electroactive molecule grafted graphene doped conductive polymer electrode materials | |
CN104362316A (en) | Lithium-sulfur battery composite cathode material, and preparation method and application thereof | |
CN104176783A (en) | Preparation method and application method for nitrogen-carbon-material-coated manganese dioxide nanowire | |
CN108258223A (en) | A kind of preparation method of the spherical N doping C coated metal oxide negative materials of multilevel hierarchy | |
CN105462365A (en) | Electric conduction nanometer copper ink preparation method | |
CN105523540A (en) | Preparation method of mesoporous carbon sphere material with controllable pore size | |
CN109437240A (en) | A kind of preparation method of kalium ion battery high potential positive electrode | |
CN103832997A (en) | Graphene/carbon black composite material, preparation method and application thereof | |
CN108448098B (en) | Positive electrode material Na of sodium-ion battery with flower-shaped structure2CoFe(CN)6Preparation method of (1) | |
CN105435843A (en) | Method for assembling and preparing novel non-precious metal electrocatalyst through bisporphyrin | |
CN107512740B (en) | A kind of lithium ion battery negative material FeVO4The preparation method of nano wire | |
CN107093709A (en) | A kind of porous carbon ball loads the preparation method of sulfide composite | |
CN104803423A (en) | Preparation method and application of porous cobaltosic oxide material | |
CN104300151B (en) | A kind of preparation method of porous carbon ball load M-Sn alloy nano particle composite |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 Termination date: 20191013 |
|
CF01 | Termination of patent right due to non-payment of annual fee |